Process for foliar fungicide treatment and fungicide composition for implementing the process

ABSTRACT

The present invention relates to a process for the control of fungal disease of plants by applying to the leaves of the plants: 
     a) 2-(4-chlorobenzylidene)-5,5-diemethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanol; 
     b) one or more fungicides suitable for protecting against the said fungal diseases and to compositions which may be used in the process.

The present invention relates to a fungicidal composition intended inparticular, for the protection of cultivated plants, comprising (a)2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanol,(b) one or more fungicides, (c) an agriculturally acceptable inertcarrier and (d) optionally an agriculturally acceptable surface-activeagent.

The invention also relates to a process for protecting plants, bycurative or prophylactic means, against fungal diseases by applying aneffective dose of a composition according to the invention or of theindividual active components (a) and (b) to the leaves of the plants.

2-(4-Chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanolis described in European Patent Application No. 89/420,520 filed on 27thDec. 1989 and unpublished to date.

The compound2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanolmay be prepared in the following manner:

100 ml of a 10% aqueous solution of sodium hydroxide were added to amixture of 10 g of 2,2-dimethylcyclopentanone and 13.8 g of4-chlorobenzaldehyde in 100 ml of ethanol at 0° C. After 30 minutes, athick slurry was filtered off and the solid washed and then dried. 12.5g of 2,2-dimethyl-5-(4-chlorobenzylidene)-1-cyclopentanone with amelting point of 120° C. were obtained. This compound, dissolved in 50ml of THF, was added to a solution formed in the following manner: 1.9 gof sodium hydride (80% dispersion in mineral oil) in 50 ml of anhydrousDMSO were heated to 80° C. until complete dissolution of the solid. Thesolution was then diluted with 100 ml of THF, then cooled to -10° C. Asolution of 11.5 g of trimethylsulphonium iodide in 80 ml of dimethylsulphoxide were added to the mixture in the course of ten minutes andthe mixture was stirred for 15 minutes at -10° C. A solution of 11.8 gof 2,2-dimethyl-4-chloro-5-(4-chlorobenzylidene)-1-cyclopentanone wasthen added in 100 ml of THF.

The mixture thus obtained was left at room temperature then poured intowater and extracted with ether, washed with water, dried and distilled.7-(4-Chlorobenzylidene)-4,4-dimethyl-1-oxaspiro[2.4]heptane, which wasdirectly used in the subsequent stage, was obtained.

A mixture of 5 g of product with 2.8 g of 1,2,4-triazole and 11 g ofpotassium carbonate was heated in 40 ml of N,N-dimethylformamide for 4hours. The mixture was poured into water and extracted with ethylacetate. The organic phase was washed, dried and recrystallized to yieldthe stated product having a melting point of 143° C.

The chemical structure of2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanolobtained is given below. ##STR1##

The structure of the compound is, in a very large majority of cases(>95%), that in which the para-chlorophenyl group is in the E positionwith respect to the carbon bearing the hydroxide group.

2,2-Dimethylcyclopentanone may be obtained in a manner which is known inthe literature or is available commercially (see Fine ChemicalDirectory).

When choosing the fungicides of component (b) suitable for theprotection of plants, those skilled in the art may usefully refer to theinformation given in reference works which state the absence ofphytotoxicity for the said products as well as their efficacy againstany particular disease.

These works include the "Index phytosanitaire" [Index ofplant-protection agents], 1990 Edition, ACTA, 75595 PARIS CEDEX 12.

The fungicide compositions according to the invention typically contain0.5 to 95% by weight of active material. As described herein, unlessotherwise specified, percentages are by weight.

The term "carrier", in the present text, designates an organic orinorganic material, natural or synthetic, with which the active materialis combined in order to facilitate its application to the plant, seedsor soil. This carrier is therefore generally inert and must beagriculturally acceptable, particularly on the treated plant. Thecarrier may be solid (clays, natural or synthetic silicates, silica,resins, waxes, solid fertilizers, and the like) or liquid (water,alcohols, ketones, petroleum fractions, aromatic or paraffinichydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like).

The surface-active agent may be an emulsifying, dispersing or wettingagent of the ionic or nonionic type. The following may be mentioned byway of example: polyacrylic acid salts, lignosulphonic acid salts,phenolsulphonic or naphthalenesulphonic acid salts, polycondensates ofethylene oxide and fatty alcohols or fatty acids or fatty amines,substituted phenols (alkylphenols or arylphenols in particular), estersalts of sulphosuccinic acids, taurine derivatives (alkyltaurates inparticular), phosphoric esters of alcohols or of polyoxyethylatedphenols. The presence of at least one surface-active agent is essentialgiven that the active material and/or the inert carrier are insoluble inwater and that the vector agent of the application is water.

These compositions may also contain other ingredients such as, forexample, protective colloids, adhesives, thickeners, thixotropic agents,penetrating agents, stabilizers, sequestrants, pigments, colorants andpolymers.

More generally, the compositions according to the invention may becombined with all those solid or liquid additives found in the usualformulation procedures.

Among the compositions, solid or liquid compositions may generally bementioned.

By way of solid composition forms, the following are included: powdersfor dusting or dispersing (with a content of active material (i.e.fungicide (a) and one or more (b) fungicides) which may be as high as100%) and granules, particularly those obtained by extrusion, bycompaction, by impregnation of a granulated carrier and by granulationfrom a powder (the content of active material in these granules beingbetween 1 and 80% in the latter cases).

The compositions may furthermore be used in the form of a powder fordusting; a composition comprising 50 g of active material, 10 g offinely divided silica and 970 g of talc may also be used; theseconstituents are mixed and ground and the mixture is applied by dusting.

By way of liquid composition forms or forms intended to constituteliquid compositions on application, the following are included:solutions, in particular water-soluble concentrates, emulsifiableconcentrates, emulsions, concentrated suspensions, aerosols, wettablepowders (or spray powder) and pastes.

The emulsifiable or soluble concentrates generally comprise 10 to 80% ofactive material; the emulsions or solutions ready for applicationcontain, for their part, 0.01 to 20% of active material.

For example, in addition to the solvent, the emulsifiable concentratesmay contain when necessary, 2 to 20% of appropriate additives such asthe stabilizers, surface-active agents, penetrating agents, corrosioninhibitors, colorants or adhesives previously mentioned.

From these concentrates, emulsions of any desired concentration, whichare particularly suitable for application to leaves, may be obtained bydilution with water.

The concentrated suspensions, which can also be applied by spraying, areprepared so as to obtain a stable fluid product which does not formdeposits, and they normally contain from 10 to 75% of active material,0.5 to 15% of surface-active agents, 0.1 to 10% of thixotropic agents, 0to 10% of appropriate additives, such as pigments, colorants, antifoams,corrosion inhibitors, stabilizers, penetrating agents and adhesives and,by way of carrier, water or an organic liquid in which the activematerial is barely soluble or insoluble: some organic solid materials orinorganic salts may be dissolved in the carrier to help preventsedimentation or as anti-freeze for water.

The wettable powders (or spray powders) are normally prepared so thatthey contain 20 to 95% of active material, and they normally contain, inaddition to the solid carrier, from 0 to 5% of a wetting agent, 3 to 10%of a dispersing agent and, when necessary, from 0 to 10% of one or morestabilizers and/or other additives, such as pigments, colorants,penetrating agents, adhesives, or anticoagulating agents, and the like.

To obtain these spray powders or wettable powders, the active materialsare thoroughly mixed in appropriate mixers with the additionalsubstances and they are ground using mills or other appropriategrinders. Spray powders are thereby obtained having wettability andability to form suspensions which are advantageous; they can besuspended in water at any desired concentration and these suspensionsmay be used very advantageously, in particular for application to plantleaves.

In place of the wettable powders, pastes may be prepared. The conditionsand methods for the preparation and the use of these pastes are similarto those for wettable powders or spray powders.

The dispersible granules are normally prepared by agglomeration, inappropriate granulation systems, of the composition of the wettablepowder type.

As already indicated, the dispersions and aqueous emulsions, forexample, the compositions obtained by diluting a wettable powder or anemulsifiable concentrate according to the invention with water, areincluded within the general scope of the present invention. Theemulsions may be of the water-in-oil or oil-in-water types and they mayhave a thick consistency like that of a "mayonnaise".

Among these compositions, those persons skilled in the art willadvantageously choose that or those which is/are suitable in relation tothe combinations chosen.

The compositions according to the invention may be used in a preventiveor curative capacity for combating fungi, particularly of thebasidiomycete, ascomycete, adelomycete or imperfect fungi types, inparticular rusts, oidium, eyespot, fusarioses, Fusarium roseum, Fusariumnivale, net blotch, leaf blotch, septoria spot, bunt, rhizoctonioses ofvegetables and plants in general and, in particular, of cereals such aswheat, barley, rye, oats and their hybrids and also rice and maize.

The compositions according to the invention are active in particularagainst fungi particularly of the following types: basidiomycetes,ascomycetes, adelomycetes or imperfect fungi such as Botrytis cinerea,Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercosporabeticola, Puccinia striiformis, Erysiphe cichoracearum, Fusariumoxysporum (melonis, for example), Pyrenophora avenae, Septoria tritici,Venturia inaequalis, Whetzelinia sclerotiorum, Monilia laxa,Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani,Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum,Helminthosporium oryzae, Penicillium expansum, Pestalozzia sp,Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma lingam,Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guignardiabidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotiniasclerotiorum, Sclerotinia minor, Coryneum cardinale, Rhizoctonia solani.

They are also and furthermore active against the following fungi:Acrostalagmus koningi, Alternaria, Colletotrichum, Diplodia natalensis,Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendroncladosporioides, Lentinus degener or tigrinus, Lenzites quercina,Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti,Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus,Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbumsp., Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

The compositions of the invention are particularly useful due to theirwide spectrum in relation to cereal diseases (oidium, rust, eyespot,leaf blotch, net blotch, septoria spot and fusarioses). They are also ofgreat interest because of their activity on grey mould (Botrytis) andleaf spot, and as a result, they can be applied to products of croppropagation as varied as vines, market garden crops, arboriculturalcrops and tropical crops such as groundnuts, banana plants, coffeeplants, pecan nuts and the like.

In addition to the applications already described above, thecompositions according to the invention further possess an excellentbiocidal activity towards numerous other varieties of microorganismsamongst which there may be mentioned, without implying a limitation,fungi such as those of the genera:

Pullularia, such as the P. pullulans species,

Chaetonium, such as the C. globosum species,

Aspergillus, such as the Aspergillus niger species,

Coniophora, such as the C. puteana species.

Because of their biocidal activity, the compositions of the inventionmake it possible to effectively combat microorganisms whoseproliferation creates numerous problems in the agricultural andindustrial sectors. To that effect, they are particularly well suited tothe protection of plants or industrial products such as timber, leather,paints, paper, rope, plastics and industrial water systems.

They are more particularly well suited to the protection oflignocellulose products and of timber in particular, whether this betimber for furniture or for building, or timber exposed to adverseweather conditions such as fencing timber, vine posts and railwaysleepers.

The compositions according to the invention are generally employed withorganic solvents and may optionally be combined with one or more knownbiocidal products such as pentachlorophenol, metal salts particularly ofcopper, manganese, cobalt, chromium and zinc derived from inorganic orcarboxylic acids (heptanoic, octanoic and naphthenic acids); tin organiccomplexes, mercaptobenzothiazole, or insecticides such as pyrethroids ororganochlorides.

The compositions may most often contain one fungicide of component (b)(binary combination) or two (ternary combination) or even four(quaternary combination).

The fungicides which are suitable within the scope of the presentinvention are advantageously chosen from among the following subclasses:

1. chlorinated or nitrated benzene derivatives such as quintozene orchlorothalonil,

2. dicarboximide derivatives such as captan, folpel, captafol,iprodione, procymidone and vinclozolin,

3. derivatives comprising one or more heterocyclic compounds such asquinolines (ethoxyquin), morpholines (dodemorph, tridemorph,fenpropimorph,4-[3-(4-chlorophenyl)-2-methylpropyl]-2,6-dimethylmorpholine describedin EP-A-262870), pyrroles such as fenpiclonil or4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile and piperidines(fenpropidin),

4. phosphorous acid derivatives such as metal phosphites such asphosetyl-A1 and phosphorous acid itself and its calcium or potassiumsalts,

5. dithiocarbamic acid derivatives such as maneb, mancozeb or zineb,

6. phenol derivatives such as dinocap or binapacryl,

7. quinone derivatives such as dithianon, chloranil, triazoxide,

8. carbamic acid and benzimidazole derivatives such as carbendazim,benomyl, thiophanate-methyl or dithiocarbamates such as thiram,

9. sulphur-containing derivatives such as dazomet or etridiazole orsulphur,

10. amines and amides such as dichloran, carboxin, triflorin, cymoxanil,metalaxyl, ofurace, oxadixyl, ampropylfos,

11. diazines such as chinomethionat, fenarimol, anilazine, nuarimol,bupirimate, ethyrimol, pyrazophos,

12. sulphamides such as dichlofluanid, tolyfluanid,

13 guanidines such as doguadine, guazatine triacette, iminoctadinedodecylbenzenesulphonate,

14. triazoles such as, for example, those described in the BritishPatent No. 2046260 whose content is incorporated by reference such asdinizconazole or other known triazoles, propiconazole, triadimefon,triadimenol, dichlobutrazol, bitertanol, penconazol, flutriafol,tebuconazol, flusilazole,

15. imidazoles such as prochloraz or imazalil,

16. copper or organic or inorganic copper derivatives such asoxine-copper.

The common names of these compounds are approved by the BritishStandards Institution and correspond to the active materials describedin The Pesticide Manual, 8th edition, 1987.

Preferably, the weight ratio of the compound of component a) to thefungicides of component (b) described above is between 0.0003 and 3,000and advantageously between 0.001 and 1,000.

The following fungicides of component (b) are preferred:

maneb,

fenpropimorph,

thiram,

iprodione,

phosethyl-Al,

ethyrimol.

The invention also provides a method for the control of fungal diseaseof a plant suffering from, or subject to, fungal disease, whichcomprises applying to the leaves of the plant (a)2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanoland (b) one or more other fungicides effective against the fungaldisease. It will be understood that the amount of active material shouldbe effective to combat fungal growth and be non-phytotoxic.

These compositions can be advantageously applied in doses of 0.002 to 1kg/ha and more specifically of 10 to 600 g/ha.

Among crops, the following may be mentioned: cereals (wheat or barley,for example), vines, market, garden crops, rice, maize, arboriculturalcrops, tropical crops, beet and rape.

The process may be implemented by using a composition which is ready foruse, or by mixing various active materials immediately before use (tankmix). The composition may also be formed in situ by successiveapplications to the leaf of the various active materials.

The invention is further illustrated by the examples given below, whichare not intended to limit the invention.

EXAMPLE 1 In vivo test on "Puccinia recondita", causative agent of brownrust in wheat

An aqueous emulsion of active material (fungicide (a) and maneb mixture)having the following composition:

test active material: 90 mg,

Tween 80 (surface-active agent composed of a sorbitanpolyoxyethylene-derivative oleate) diluted to 10% in water: 0.45 ml,

water: 90 ml

is prepared by grinding the components finely.

This aqueous emulsion is then diluted with water to obtain the desiredconcentration.

Wheat, sown in pots of loam, is treated at the stage when it is 10 cmhigh by spraying with aqueous emulsions (called sprays) of the samecomposition as that described above and at various concentrations of thetest compound. The trial is repeated twice for each concentration.

After 24 hours, an aqueous suspension of spores (50,000 sp/cm³) issprayed onto the wheat; this suspension was obtained from contaminatedplants. The wheat is then placed for 48 hours in an incubation cell atabout 18° C. and about 100% relative humidity.

After these two days, the relative humidity is brought to 60%. Thecondition of the plants is monitored between the 11th and 15th day afterthe contamination by comparison with the untreated control.

Under these conditions, the following results are observed:

    ______________________________________                                        Per cent efficacy                                                                    mg/1 MANEB                                                             Fungicide (a)                                                                          0      4        12   37     111  333                                 ______________________________________                                         0       0      27.5     32.5 72.5   95   97.25                                4       0      18.75    40   52.5   76.25                                                                              95.25                               12       36.25  36.25    42.5 62.5   81.25                                                                              98                                  37       57.5   65       75   85     92.5 98.5                                111      80     80       81.25                                                                              85     90   98.5                                333      95.7   98       97.75                                                                              98.25  98.75                                                                              100                                 ______________________________________                                    

EXAMPLE 2 In vivo test on "Erysiphe graminis" f.sp. hordei responsiblefor oidium in barley

A combination of the (a) fungicide and fenpropimorph is preparedaccording to the preceding method.

Barley, sown in pots of loam, is treated at the stage when it is 10 cmhigh by spraying with an aqueous emulsion (called spray) at theconcentration indicated hereafter. The trial is repeated twice. After 24hours, the barley plants are dusted with Erysiphe graminis spores, thedusting being carried out using diseased plants.

Readings are made 8 to 12 days after the contamination.

Under these conditions, the following results are observed:

    ______________________________________                                        Per cent efficacy                                                             mg/1                                                                                  FENPROPIMORPH                                                         Fungicide (a)                                                                           0      4        12   37     111  333                                ______________________________________                                         0        0      26.25    38.75                                                                              56.25  67.5 83.75                               4        38.75  52.5     52.5 53.75  55   67.5                               12        61.25  52.5     52.5 52.5   75   80                                 37        62.5   63.75    67.5 65     71.25                                                                              90                                 111       68.75  55       67.5 75     86.25                                                                              92.5                               333       75     90.75    99.5 93.75  98.5 96                                 ______________________________________                                    

We claim:
 1. A process for the treatment of a plant suffering from, orprotection of a plant subject to, fungal diseases which comprisesapplying to the leaves of the plant a fungicidal and non-phytotoxicamount of a component (a)2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanoland a component (b) at least one dithiocarbamic acid derivativefungicide, wherein the proportion by weight of component (a) tocomponent (b) is from 0.0003 to 3,000, inclusive.
 2. A process for thetreatment of a plant suffering from, or protection of a plant subjectto, fungal diseases which comprises applying to the leaves of the planta fungicidal and non-phytotoxic amount of a fungicidal compositioncomprising a component (a)2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanol,a component (b) at least one dithiocarbamic acid derivative fungicideand an agriculturally acceptable carrier, wherein the proportion byweight of component (a) to component (b) is from 0.0003 to 3,000,inclusive.
 3. The process according to claim 1, wherein the fungaldiseases are diseases of cereals, vines, market garden crops,arboricultural crops, tropical crops, rice, maize, beet or rape.
 4. Theprocess according to claim 2, wherein the fungal diseases are diseasesof cereals, vines, market garden crops, arboricultural crops, tropicalcrops, rice, maize, beet or rape.
 5. The process according to claim 1whereinthe dithiocarbamic acid derivative is selected from the groupconsisting of maneb, mancozeb and zineb.
 6. The process according toclaim 2, whereinthe dithiocarbamic acid derivative is selected from thegroup consisting of maneb, mancozeb and zineb.
 7. The process accordingto claim 1, wherein the proportion by weight is from 0.001 to 1,000,inclusive.
 8. The process according to claim 2, wherein the proportionby weight is from 0.001 to 1,000, inclusive.
 9. The process according toclaim 1, wherein the amount of component (a) and component (b) appliedis 0.002 to 1 kg/ha.
 10. The process according to claim 2, wherein theamount of component (a) and component (b) applied is 0.002 to 1 kg/ha.11. The process according to claim 9, wherein the amount applied is 10to 600 g/ha.
 12. The process according to claim 10, wherein the amountapplied is 10 to 600 g/ha.
 13. The process according to claim 2 whereinthe fungicidal composition further comprises an agriculturally suitablesurface-active agent.
 14. The process according to claim 5, wherein thedithiocarbamic acid derivative is maneb.
 15. The process according toclaim 6, wherein the dithiocarbamic acid derivative is maneb.
 16. Acomposition for the protection of a plant suffering from, or subject to,fungal diseases comprising a component (a)2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1-cyclopentanol,a component (b) at least one dithiocarbamic acid derivative fungicideand an agriculturally suitable inert carrier, wherein the proportion byweight of component (a) to component (b) is from 0.0003 to 3,000,inclusive.
 17. The composition according to claim 16, whereinthedithiocarbamic acid derivative is selected from the group consisting ofmaneb, mancozeb and zineb.
 18. The composition according to claim 16,wherein the proportion by weight is from 0.001 to 1,000, inclusive. 19.The composition according to claim 17, wherein the dithiocarbamic acidderivative is maneb.
 20. The composition according to claim 16 furthercomprising an agriculturally suitable surface-active agent.